US4590309A - Process for the preparation of perfluoroalkanols - Google Patents

Process for the preparation of perfluoroalkanols Download PDF

Info

Publication number
US4590309A
US4590309A US06/727,621 US72762185A US4590309A US 4590309 A US4590309 A US 4590309A US 72762185 A US72762185 A US 72762185A US 4590309 A US4590309 A US 4590309A
Authority
US
United States
Prior art keywords
metal
sub
group
additive
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US06/727,621
Other languages
English (en)
Inventor
Georges Cordier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhone Poulenc Specialites Chimiques
Original Assignee
Rhone Poulenc Specialites Chimiques
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhone Poulenc Specialites Chimiques filed Critical Rhone Poulenc Specialites Chimiques
Application granted granted Critical
Publication of US4590309A publication Critical patent/US4590309A/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases

Definitions

  • the present invention relates to a process for the preparation of perfluoroalkanols; it relates more particularly to a process for the preparation of perfluoroalkanols by hydrogenation of the corresponding perfluorinated aliphatic acids.
  • French Patent Application 70/31,913, published under No. 2,060,357 is known in the prior art and describes the preparation of 1,1-dihydroperfluoroalkanols corresponding to the general formula C n F 2n+1 CH 2 OH, in which n ⁇ 3, by the hydrogenation of acids or esters of the formula C n F 2n+1 COOR, in which R represents a hydrogen atom or an alkyl radical and in which n ⁇ 3, in the presence of a ruthenium-based catalyst.
  • the hydrogenation is carried out in the presence of 4 to 1000% by weight of water, relative to the acid or ester, and under a high temperature and a high hydrogen pressure.
  • the temperature is between 80 and 240° C. and the initial hydrogen pressure varies between 5 and 700 kgp/cm 2 .
  • U.S. Pat. No. 4,273,947 is also known, which describes a process for the hydrogenation of trifluoroacetic acid (CF 3 COOH) in which this acid is brought into contact with hydrogen in the liquid phase, in the presence of a supported or unsupported catalyst based on rhodium or iridium, under a pressure of 5 to 15 atmospheres and at a temperature of 50 to 150° C.
  • CF 3 COOH trifluoroacetic acid
  • the inventor has now discovered a process making it possible to minimize and even to eliminate these secondary reactions, which are also the cause of a considerable loss of yield.
  • the invention therefore relates to a process for the preparation of perfluoroalkanols by hydrogenation of the corresponding aliphatic perfluoroacids, which comprises reacting an acid of the formula:
  • n is greater than or equal to 1, with hydrogen, in the presence of a catalyst based on ruthenium, rhodium, iridium or platinum, under a total pressure of between 1 and 50 bar and in the presence of at least one additive chosen from the group comprising the halide anions and the metal cations of columns IB, IIB, IVA, VA and VB of the periodic table of the elements.
  • a quantity of additive of between 0.001 and 10 gram atoms per gram atom of catalyst metal, i.e. per gram atom of ruthenium, rhodium, iridium or platinum. Even more preferably, this quantity is between 0.01 and 1 gram atom.
  • the metal cation is preferably chosen from the cations of the metals of columns IB, IIB, IVA, VA and VB of the periodic table of the elements. Even more preferably, it is derived from the following metals: Cu, Ag, Cd, Hg, Sn, Pb, Sb, Bi and Ta. It is very particularly preferred to use the cations derived from Pb and Ta.
  • the metal cation is preferably used in the form of a salt or an oxide.
  • a salt or an oxide examples which may be mentioned are: tantalum pentoxide, Ta 2 O 5 , bismuth oxide, Bi 2 O 3 , tin oxide, SnO 2 , the acetates and trifluoroacetates of Pb 2+ , Cu 2+ , Hg + and Cd 2+ , or carbonates (Ag 2 CO 3 ) and the sulfates of Cu 2+ and Cd 2+ .
  • the halide anion is preferably used in the form of the corresponding hydrogen acid (HCl, HF, HBr and HI), the halide of the abovementioned metals of columns IB, IIB, IVA, VA and VB or the halide of the alkali metals and alkaline earth metals of columns IA or IIA of the periodic table.
  • Examples which may be mentioned are: the fluorides, chlorides, bromides and iodides of lithium, sodium, potassium, calcium and magnesium.
  • the invention is particularly suitable for carrying out the hydrogenation reaction under a pressure of between 5 and 30 bar.
  • the catalysts used within the scope of the process according to the invention can be in the form of the metal itself or in the form of an oxide or a salt, or a mixture of these. Furthermore, they may or may not be deposited on a support.
  • any support which is inert under the reaction conditions such as charcoal, silica or alumina.
  • charcoal will be very particularly preferred.
  • the quantity of metal deposited on the support is preferably between 0.1 and 20% by weight and more preferably between 1 and 10%.
  • catalysts which may be mentioned are: ruthenium, rhodium, iridium or platinum in the form of the metal, their oxides, hydroxides and salts with acids (nitrates, sulfates and acetates) and mixtures of these, if appropriate deposited on charcoal or silica.
  • rhodium metal deposited in a proportion of 5% on charcoal is used.
  • the reaction is preferably carried out at a temperature of between 20° and 200° C. Even more preferably, the temperature is between 70° and 150° C.
  • the quantity of catalyst used (expressed in % of the metal) is preferably less than 10% by weight, relative to the aliphatic perfluoroacid. Even more preferably, less than 2% of catalyst is used.
  • the reaction preferably takes place in the presence of a solvent. However, it is not excluded to carry out the reaction without a solvent. Water or an inert organic compound (for example an alkane) can be used. Water facilitates the use of catalysts which are generally sold moist.
  • the invention is particularly advantageous for obtaining trifluoroethanol by hydrogenation of trifluoroacetic acid.
  • the pressure in the reactor is brought to 45 bar and the reactor is heated to 120° C.
  • the reaction starts while the temperature is rising and the consumption of hydrogen thus compensates for the pressure increase associated with the expansion of the gases.
  • the hydrogen necessary for the reaction is then fed in continuously, the pressure being kept constant at 45 bar. The reaction stops after 2 hours 10 minutes.
  • the reaction is stopped after 200 minutes.
  • the degree of conversion of the trifluoroacetic acid is 97.5% and the yield of trifluoroethanol is 98%.
  • the yield of CF 3 CH 3 is 1.2% and that of methane is 0.06%.
  • Example 2 is repeated, 10 times the quantity of Pb(CH 3 COO) 2 .3H 2 O being introduced.
  • the degree of conversion of the trifluoroacetic acid is 96.5% and the yield of trifluoroethanol is 100%. There are no longer any heavy fluorinated gases and only traces of methane are found.
  • the reaction is carried out in the manner stated in Example 1, but at 150° C./total pressure of 20 bar. It stops after 85 minutes.
  • the degree of conversion of the trifluoroacetic acid is 99.3%.
  • the yield of trifluoroethanol is 93.5%.
  • Example 4 is repeated, 20 mg of copper acetate, Cu(CH 3 COO) 2 .H 2 O, being added to the reaction medium, i.e. a ratio Cu 2+ /Rh of 0.5.
  • the reaction stops after 2 hours at 150° C. and under a total pressure of 20 bar.
  • the degree of conversion of the trifluoroacetic acid is 48.6% and the yield of trifluoroethanol is 97.5%.
  • Example 5 is repeated, the cupric acetate being replaced with 0.003 g of stannous sulfate, Sn(SO 4 ), i.e. Sn 2+ /Rh:0.07. After a reaction time of 6 hours 50 minutes at 150° C. and under a pressure of 20 bar, the reaction stops. The degree of conversion of the trifluoroacetic acid is 94% while the yield of trifluoroethanol is 97.2%.
  • Example 5 is repeated, 0.016 ml of an aqueous solution of HI containing 1 mol/liter being added to the reaction medium.
  • Example 5 is repeated, 0.16 ml of an aqueous solution of HCl containing 1 mol/liter being added to the medium.
  • the reaction is carried out at 150° C. and under a total pressure of 50 bar. It stops after 30 minutes.
  • Example 9 is repeated with half the quantity of the same catalyst, 0.481 g of cadmium sulfate (3CdSO 4 .8H 2 O) being added to the medium, i.e. a ratio Cd/Ru of 4.
  • the degree of conversion of the trifluoroacetic acid is 97% and the yield of trifluoroethanol is 93.5%.
  • the degree of conversion of the trifluoroacetic acid is 52.5% and the yield of trifluoroethanol is 96.3%.
  • the degree of conversion of the trifluoroacetic acid is 52.5% and the yield of trifluoroethanol is 96.5%.
  • the degree of conversion of the trifluoroacetic acid is 97.9%.
  • the yield of trifluoroethanol is 95.8% while the yields of gaseous by-products are:
  • the degree of conversion of the trifluoroacetic acid is 98.3% while the yield of trifluoroethanol is 97.1%.
  • Example 10 is repeated, the cadmium sulfate being replaced with 0.5 ml of an aqueous solution of HCl containing 0.1 mol/liter, and the reaction is carried out at 140° C. and under a pressure of 37 bar.
  • the degree of conversion of the trifluoroacetic acid is 98.4%.
  • the yield of trifluoroethanol is 94.5%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Medicinal Preparation (AREA)
US06/727,621 1983-05-06 1985-04-30 Process for the preparation of perfluoroalkanols Expired - Fee Related US4590309A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8307569 1983-05-06
FR8307569A FR2545481B1 (fr) 1983-05-06 1983-05-06 Procede de preparation de perfluoroalcanols

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US06596939 Continuation 1984-04-05

Publications (1)

Publication Number Publication Date
US4590309A true US4590309A (en) 1986-05-20

Family

ID=9288653

Family Applications (1)

Application Number Title Priority Date Filing Date
US06/727,621 Expired - Fee Related US4590309A (en) 1983-05-06 1985-04-30 Process for the preparation of perfluoroalkanols

Country Status (9)

Country Link
US (1) US4590309A (enrdf_load_stackoverflow)
EP (1) EP0128059B1 (enrdf_load_stackoverflow)
JP (1) JPS604143A (enrdf_load_stackoverflow)
AT (1) ATE20048T1 (enrdf_load_stackoverflow)
BR (1) BR8402097A (enrdf_load_stackoverflow)
CA (1) CA1221387A (enrdf_load_stackoverflow)
DE (1) DE3460176D1 (enrdf_load_stackoverflow)
ES (1) ES532174A0 (enrdf_load_stackoverflow)
FR (1) FR2545481B1 (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040030199A1 (en) * 2002-01-29 2004-02-12 Maughon Robert R. Process for reducing alpha-haloketones to secondary alpha-haloalcohols
CN104829432A (zh) * 2015-03-18 2015-08-12 武汉工程大学 一种制备氟代醇的方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2612178B1 (fr) * 1987-03-12 1989-07-21 Inst Francais Du Petrole Procede de fabrication d'alcools par hydrogenolyse d'esters d'acides carboxyliques en presence d'un catalyseur contenant du ruthenium et de l'etain, du germanium ou du plomb
FR2638158B1 (fr) * 1988-10-21 1991-04-12 Rhone Poulenc Chimie Procede de preparation de trifluoroethanol
JPH0614590U (ja) * 1992-07-31 1994-02-25 三ツ星ベルト株式会社 極薄平ベルト

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2862977A (en) * 1956-12-21 1958-12-02 Du Pont Hydrogenation of perfluoroalkanoic acids to 1, 1-dihydroperfluoroalkyl alcohols over ruthenium catalyst
US3318662A (en) * 1960-10-17 1967-05-09 Metallgesellschaft Ag Sulfur dioxide separation
US3390191A (en) * 1964-03-24 1968-06-25 Allied Chem Hydrogenation of methyl trifluoroacetate to trifluoroethanol
FR2060357A1 (enrdf_load_stackoverflow) * 1969-09-02 1971-06-18 Hoechst Ag
US4273947A (en) * 1979-01-31 1981-06-16 Allied Chemical Corporation Hydrogenation of fluorine-containing carboxylic acids
US4396784A (en) * 1980-06-24 1983-08-02 Phillips Petroleum Company Hydrogenation of fluoroacids with rhenium-fluorided alumina catalyst

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2222682A1 (de) * 1972-05-09 1973-11-22 Hoechst Ag Verfahren zur hydrierung von perfluoralkancarbonsaeuren

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2862977A (en) * 1956-12-21 1958-12-02 Du Pont Hydrogenation of perfluoroalkanoic acids to 1, 1-dihydroperfluoroalkyl alcohols over ruthenium catalyst
US3318662A (en) * 1960-10-17 1967-05-09 Metallgesellschaft Ag Sulfur dioxide separation
US3390191A (en) * 1964-03-24 1968-06-25 Allied Chem Hydrogenation of methyl trifluoroacetate to trifluoroethanol
FR2060357A1 (enrdf_load_stackoverflow) * 1969-09-02 1971-06-18 Hoechst Ag
US3663629A (en) * 1969-09-02 1972-05-16 Hoechst Ag Process for the preparation of 1,1-dihydroperfluoroalkanols
US4273947A (en) * 1979-01-31 1981-06-16 Allied Chemical Corporation Hydrogenation of fluorine-containing carboxylic acids
US4396784A (en) * 1980-06-24 1983-08-02 Phillips Petroleum Company Hydrogenation of fluoroacids with rhenium-fluorided alumina catalyst

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040030199A1 (en) * 2002-01-29 2004-02-12 Maughon Robert R. Process for reducing alpha-haloketones to secondary alpha-haloalcohols
CN104829432A (zh) * 2015-03-18 2015-08-12 武汉工程大学 一种制备氟代醇的方法

Also Published As

Publication number Publication date
EP0128059A2 (fr) 1984-12-12
ATE20048T1 (de) 1986-06-15
CA1221387A (fr) 1987-05-05
JPS6240345B2 (enrdf_load_stackoverflow) 1987-08-27
BR8402097A (pt) 1984-12-11
EP0128059A3 (en) 1985-01-09
FR2545481A1 (fr) 1984-11-09
ES8502073A1 (es) 1984-12-16
ES532174A0 (es) 1984-12-16
FR2545481B1 (fr) 1985-07-19
EP0128059B1 (fr) 1986-05-28
JPS604143A (ja) 1985-01-10
DE3460176D1 (en) 1986-07-03

Similar Documents

Publication Publication Date Title
US5625094A (en) Rhodium/iridium catalyzed synthesis of carboxylic acids or esters thereof
EP0425197B1 (en) Process for preparing diester of carbonic acid
US3769329A (en) Production of carboxylic acids and esters
EP0284310B1 (en) Process for producing ibuprofen
US5231213A (en) Process for the preparation of dialkyl carbonates
US4590309A (en) Process for the preparation of perfluoroalkanols
EP0087869B1 (en) Process for the coproduction of carboxylic acids and acid anhydrides
JPS58118527A (ja) カルボン酸およびカルボン酸エステルの同時製造方法
GB1567594A (en) Process for preparing carboxylic acids
US5498806A (en) Process for preparing 1-chloro-1,2,2-trifluoroethylene or 1,2,2-trifluoroethylene
US3848065A (en) Method for producing hydrogen iodide
EP0459463A1 (en) Process for preparing 1-chloro-1,2,2-trifluoroethylene or 1,2,2-trifluoroethylene
EP0365083B1 (en) Continuous process for preparing di-alkyl carbonates
EP0144935B2 (en) Production of carboxylic acids from alcohols
EP0501507B1 (en) Process for preparing diester of carbonic acid
EP0096974B1 (en) Process for the production of one or more carboxylic acid anhydrides
EP0060695B1 (en) Process for the coproduction of a c2 to c10 monocarboxylic acid and formic acid
EP0636599A1 (en) Process for the carbonylation of methanol to form acetic acid, methyl acetate and acetic anhydride
JP2887278B2 (ja) １―クロロ―１，２，２―トリフルオロエチレンおよび１，２，２―トリフルオロエチレンの製造方法
JPH0343257B2 (enrdf_load_stackoverflow)
EP0366177A1 (en) Improved process for preparing di-alkyl carbonates
US3358016A (en) Preparation of alkenyl esters from alkenyl chlorides and metal carboxylates in the presence of palladous chloride
US3784518A (en) Method for producing alkyl iodides
US5936117A (en) Carbonylation of olefins
US4351972A (en) Process for making anhydrous alkyl iodides

Legal Events

Date Code Title Description
REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 19900520